CA1269194A - Copolymers and blends of polymers with conjugated p- system - Google Patents
Copolymers and blends of polymers with conjugated p- systemInfo
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- CA1269194A CA1269194A CA000481074A CA481074A CA1269194A CA 1269194 A CA1269194 A CA 1269194A CA 000481074 A CA000481074 A CA 000481074A CA 481074 A CA481074 A CA 481074A CA 1269194 A CA1269194 A CA 1269194A
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- Prior art keywords
- copolymers
- groups
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- component
- ferrocene
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/26—Incorporating metal atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/06—Oxidation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Abstract:
The invention relates to electrically conductive copolymers and blends of polymers with conjugated .pi. systems with conventional non-conductive polymers carrying isolated redox-active groups. In more detail, the copolymers and blends are essentially composed of polymeric Components (A) without conjugated .pi. systems and polymeric components (B) with conjugated .pi. systems, wherein the Component (A) contains redox-active groups which possess an active potential in oxidized or reduced states, which is sufficient for the oxidation or reduction of the Component B. The new materials thus produced have specific electrical, electrochemical and chemical properties, combined with thermoplastic process-ibility and a behavior typical of plastics.
The invention relates to electrically conductive copolymers and blends of polymers with conjugated .pi. systems with conventional non-conductive polymers carrying isolated redox-active groups. In more detail, the copolymers and blends are essentially composed of polymeric Components (A) without conjugated .pi. systems and polymeric components (B) with conjugated .pi. systems, wherein the Component (A) contains redox-active groups which possess an active potential in oxidized or reduced states, which is sufficient for the oxidation or reduction of the Component B. The new materials thus produced have specific electrical, electrochemical and chemical properties, combined with thermoplastic process-ibility and a behavior typical of plastics.
Description
-- ~26931~
Description The invention concerns copolymers and blends with conjugated ~ system, methods for their production and their application.
s Polymers with conjugated ~ system, which become elec-trically conductive after doping, i. e. oxidation or reduction, can also be regarded as redox-active polymers. Oxidation or reduction of these materials means electron loss or gain by the ~ electron system of the main chain. The resultant charges are delocalized over wide ranges of ~ conjugation. They can migrate or jump along or between the chains, thus causing charge transport and thus conductivity upon application of an electric field. Electronically, thev change the band structure from the semiconducting or insulating state of the undoped polymer to that of a metal with extended partly filled band at the Fermi limit. Structurally, they form rigid microcrystalline regions which are de-trimental to all properties typical of plastics and to all mechanical and processing properties. An in-trinsically conductive polymers of this type can neither be dissolved nor melted and can only be used in the form which it adopts after doping. In order to obtain nevertheless mechanically suitable and pro-cessible electrically conductive polymers, polymers with conjugated ~ system have to be blended as block or graft copolymers or as blends with conventional macromolecules forming flexible soft segments. High conductivity, combined with good mechanical properties and processibility, is always achieved if the maximum possible homogenous distributlon of the conductive component in the matrix of the conventional polymer ~2~9~
is reached. Copolymers and blends of polyacetylene of this type are already known (Galvin and Wnek, J. of Polym.
Sci., Polym. Chem. Ec. 21, 2727 (1983); Lee and Jopson, Makrom. Chem. Rapid Commun. 4, 375 (1983)). With concen-trations as low as 5%, conductivities are reached whichare by a maximum of one to two orders of magnitude below the conductivity of pure polyacetylene. The oxidatively doped conductive polyacetylene, however, has the drawback to decompose on storage and in air, thus losing its conductivity.
It is the object of the present invention to produce intrinsically conductive polymers which are stable and have optimum processing properties.
According to the invention, this aim is reached by the fact that the copolymers and blends are essentially composed of polymeric components (A) without conjugated~
system and of polymeric components (B) with conjugated~
system, the component A containing redox-active groups which, in oxidized or reduced state, have an active potential that is sufficient for oxidation or reduction of the component ~.
In the methods of producing suc'n copolymers and blends according to the invention, redox-active compounds are homo- or copolymerized with polymerizable substituents or attached to polymers without conjugated ~ system in 3 known manner by chemical reaction, and the polymeric component A which is thus obtained is mixed in a known manner with the polymeric component B or with the monomer forming the component B, or chemically or electrochemically oxidized or reduced.
~' ~z~
The copolymers and blends according to the invention are suitable in particular as conductors or semiconductors, in solar cells, for antistatic finish of plastics, as materials of low surface resistance, suitable for capac-itive scanning, as materials for electromagnetic shield-ing, as battery electrodes, as electrode materials and as membranes for electrochemistry and fuel cells.
The invention permits in particular polypyrrole, polythio-phene and derivatives, such as substituted polypyrroles or polythiophenes, polymers consisting of aromatic rings, pyrrole and/or thiophene units, as well as polyanilines which are obtained by oxidative polymerization of aniline, to be processed with non-conductive polymers ~'10 S/cm) in a wide range of variation to give copolymers or blends.
Almost all conventional polymers, especially those with flexible or highly mobile chain forms, can be processed as copolymers with polypyrrole to give electrically conductive plastics. This is possible on condition that redox-active groups are present, which can be either attached as side-chain substituents or incorporated by polymerization into the main chain as a difunctional monomer. Suitable redox-active groups are in particular such groups which can be oxidized and reduced with high reversibility and whose oxidation potentials are slightly above that of the poly-mers with conjugated ~ system. For polypyrrole, polyani-line and polymers composed of alternating aromatic and pyrrole rings, this is ideally reached by the dicyclopenta-dienyliron or ferrocene complex.
,~
~69~
The ferrocene complex can be reversibly oxidized at about + 0.4 to 0.5 V versus saturated colomel electrode and is capable in this form, i. e. as ferricinium salt, to oxidize the above polymers with conjugated ~ .ystem and to ma~e them conductive.
Polypyrrole, for example, has an oxidation potential of -0.2 V versus saturated colomel electrode and poly-aniline has an oxidation potential of +0.1 V versus SCE.
In the reaction with polymer-bonded ferricinium salt, electrons are transferred to the ferrocene, and anions to the polymer with conjugated ~ system:
I Fel CiO4 - +
CH ~ CH ~
I ~ C~04 -25 Nevertheless, ferrocene as redox-active group in a blend consisting of polyphenylene pyrrole or poly-naphthalene pyrrole, permits electron and ion migration even in the non-conductive part, thus causing fast and uniform doping of the conjugated polymer, which is not limited to freely accessible parts of the conductive component.
An essential feature of the invention is the bond of the ferrocene vla substituents or directly to the cy-3~Z6~
clopentadienyl rings as substituent to the side chain of a conventional polymer, or a polymer in which a disubstituted ferrocene monomer is incorporated in the main chain by polycondensation, polyaddition or aromatic substitution at the cyclopentadienvl rings.
Bonding as side-chain substituent is possible, for example, by reacting polyvinyl chloride, polybuta-diene, polyacrylate, polymethacrylate, copolymers from maleic anhydride and styrene, copolymers from butadiene and styrene, chloromethylated polystyrene or the like with AlCl3 and unsubstituted ferro-cene. Depending on the ferrocene concentration, on the use of AlCl3, in the temperature and on the course of reaction, weakly substituted non-cross-linked or highly substituted cross-linked polymers are ob-tained. Bonding of the ferrocene can also be achieved by diazotization of the poly-p-aminostyrene and subse-quent reaction with ferrocene of ferricinium salts, by reaction of the ferrocenecarboxylic acid chloride with polymers containing NH2 or OH groups, e. g. polyvinyl alcohol and copolymers such as partially hydrolyzed polyvinyl acetate or polyvinyl butyral, and in addition poly (1-hydroxypropene-(2)), polyhydroxyethyl- or hydro-xypropyl acrylate or methacrylate and copolymers there poly(1-aminopropene-(2)), poly(p-aminostyrene), poly (p-amino-o~-methylstyrene), polyvinyl amine and copoly-mers thereof, as well as copolymers of aminopropyl-triethoxysilane and siloxane oligomers.
It is also possible to attach hydroxylkyl ferrocene to copolymers which contain carboxylic acid chloride, sulfonic acid chloride or anhydride substituents, or by esterification of copolymers of acrylic acid.
~5 ~Z~91Q4 Introduction of the ferrocene molecule into the side chain of polymers is also possible by mono- or copoly-merization of monomers which contain the ferrocene ring with substituted polymerizable group. Candidates for this procedure include vinyl and divinyl ferrocene, ferrocenyl methyl methacrylate or acrylate, ferrocenyl methyl arcylamide, ethimylferrocene, p-ferrocenyl styrene, p-ferrocenyl phenylacetylene, etc.
Incorporation of ferrocene into the main chain can be achieved, for example, by polycondenzation or poly-addition with appropriate sutstituents. It is possible, e. g., to react terminally diamino- or dihydroxy-substituted monomers or prepolymers with ferrocene-dicarboxylix acid, dicarboxylic acid esters or dicarboxylic acid chloride, ferrocene diisocyanate or ferrocene dialkyl oxirane.
Inversely, dihydroxyalkvl ferrocenes can be reacted with monomeric dicarboxylix acids or polyesters with terminal carboxyl groups, with monomeric or oligo-meric diisocyanates or prepolymeric epoxy resins to give polymers with ferrocene complex in the main chain.
Like ferrocenes, it is also possible according to the invention to use other transition metal complexes, f F II/III CoII/III and RuII/III, which are attached to a polymer chain via ligands and shows reversible redox behavior. 0 Iron, cobalt or ruthenium salts complexed by poly(4)-(or-2-)-vinylpyridine or polyvinylbipyridine, for example, are suitable. According to the invention, it is possible to use polymer-bonded metal salicylates, 5 12~
metal salicylaldehvde, metal salicyl-aldehydimine complexes, Pfeiffer complexes complexed via amino acids, and the like. Preferably, polymer-bonded metal oxinates metal glyoximates, metal porphyrin and metal phthalocvanine complexes can be used. In this context, an anodic polymerizate of pyrrole and tetrasulfonated phthalocyanine iron complex (R.A.
Bull, F.R. Fan, A.J. Bard, J. Electrochem. Soc. ABC
1636, 1983) is known. In this case, however, the redox-active complex is directly incorporated in polypyrrole and not coupled with another conventional polymer.
According to the invention, also polymers with rever-sibly oxidizable and recudible organic groups can be used for the production of copolymers or blends.
In particular, polymers with quinoidal systems in main and side chains can be used, e. g. a polybenzoquinone-tetracarboxylic acid anhydride which reacts with hexa-methylenediamine to give benzoquinone main-chain poly-mers or with poly-p-aminostyrene to give side-chain polymers.
For combining the described redox-active polymers with polymers which contain a conjugated ~-electron system, it is necessary to harmonize the oxidation and reduction potentials.
The electroactive state of the polymer with isolated redox-active groups can only be utilized if the oxi-dation potential of the polvmer with conjugated ~
system is lower, or its reduction potential is higher that that of the copolymers. The polymer with redox-~26~
active groups must be able either in oxidized state to oxidize the conjugated polymer and thus make it electronically conductive, or in reduced state to reduce a polymer with conjugated ~ system.
~olymer-bonded ferrocene, therefore, can be ideally used as copolymer or blend for polypyrrole, which they cannot polymerize but oxidize and make conductive.
These polypyrrole blends are prepared according to the invention by oxidizing a homogenous mixture of a dissolved or swollen ferrocene polymer together with pyrrole, either anodically or chemically.
Electrochemically, at potentials of +0.4 to 0.6 V
versus saturated colomel electrode, the ferrocene units are first oxidized to positively charged ferricene units, whereas at 0.9 to 1.1 V polymeri-zation of pyrrole stars. As soon as the polypyrrole has reached a specific length of conjugation it is oxidized by ferricene into the conductive form, with electron and ion transfer. ~niform dustribution of ferrocene in the matrix of the conventional polymer is a prerequisite for an equally homogenous distri-bution of the polypyrrole. About 5 wf % or 1 to 2 mole % ferrocene is sufficient in the case of uniform distribution to generate conductivities of 10 2 to S/cm with about 4 to 8 mole % polypyrrole.
According to the invention, the contents of the redox-active component and the concentration of the conductive polymer are variable within a wide range from about 1 to 90 %. For the electrochemical pro-duction, solvents such as acetonitrile, propylene carbonate, nitromethane, dioxane, 1,2-dimethoxyethane, N-methylpyrrolidone, hexamethyl phosphoric acid triamide ~26~
g or the like are suitable at low water content, together with the tetraalkyl ammonium or lithium salts which are soluble therein. The polvmerization of pyrrole and the production of blends is also possible from acid aqueous solution. The anions must be resistant to oxidation and must not be below a minimum size. ~F4, C104, AsF6, SbF6, PF6, SbC16, NO3, ReO4, TaF 6' HSO4, for example, as well as organic benzene or alkane sulfonic acid anions are suitable. According to the invention, blends of ferrocene polymers and poly-pyrrole can also be produced by chemical oxydation. This is achieved preferably by iron-III salts in pure organic or aqueous/organic solution or dispersion. FeC13 or Fe(C104)3 . 9 H20, but also other oxidants such as bichromate or H202 solution, are suited for this purpose.
Reaction with the ferrocene polymer/pyrrole mixture is preferably effected in acetonitrile or in the two-phase system methylene chloride/water.
A special variant of this invention consists in using a copolymer with ferrocenyl and carboxylic acid or sul-fonic acid substituents, in which - on oxidation - the charges of the oxidized ferrocene and of the polypyrrole can be compensated by the acid anions of the polymer.
According to the invention, this can be achieved by chemical oxidation by iron-III-acetylacetonate or by electrochemical oxidation, protons and electrons being released by the polymer.
While polymer-bonded ferrocenes have sufficiently high oxidation potentials for polypyrrole and polyaniline, polymer-bonded iron-III, cobalt-III or ruthenium-III 5 ~Z69~
complexes of higher electrochemical potential are necessary for polvthiophene. Similarly, N-phenyl-substituted pyrroles can only be satisfactorily pro-cessed to copolymers or blends with these materials.
The process is equal to that used for the production of blends from polvpyrrole and ferrocene polymers.
The copolymers and blends according to the invention show good mechanical and application-technological properties. They can be processed either from the solution during production or thermoplastically molded into various shapes. If appropriate copolymers and ferrocene concentrations are selected, they can be processed into shapes with smooth surface of high electrical conductivity. They can thus be used for applications involving the electrooptical or capa-citive scanning of a surface structure. In this respect, they are also superior to black- or metal-filled plastics.
Another important application is the use of the co-polymers according to the invention as battery of fuel cell electrodes. This possible since a highly rever-sible redox system is combined with a conductive poly-mer. Oxidation and reduction cycles of the redox-active component can be used ideally for electro-chemical storage purposes. While the electrochemical-catalytic effect is used in fuel cells, it is also possible to use the copolymers and blends as chemical catalysts with active transition metal centers. Further applications are as conductors or semiconductors of low density, as materials for electromagnetic shielding, as solar cells or for antistatic finish of plastics.
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Examole _ a) Preparation of Ferrocenyl Butadiene 8.5 g AlCl3 is dissolved in 200 ml dichloroethane, then 46.5 g ferrocene is added, and 5~ g Lithene PM (Metall-gesellschaft) dissolved in 200 ml dichloroethane is added dropwise. After stirring for two hours at room temperature, the reaction mixture is poured into 600 ml methanolic HCl, the polymer is separated by filtration, washed and dried. The starting polymer is first oxidized with FeCl3 in nitromethane, washed and then used for preparing the blend.
b) Reaction with Pyrrole Ferrocenyl butadiene in oxidized form is swollen in di-chloroethane together with pyrrole and subsequently reaction with aqueous iron-III-perchlorate solution in a two-phase reaction. The resultant blend is pre-cipitated with methanol, washed and dried. It shows thermoplastic properties and elastic behavior. Con-ductivity: 10 2 S/cm.
Example 2 a) Preparation of Ferrocenyl Polystyrole 6 g poly-p-aminostyrene is suspended in 100 ml 10-%
aqueous sulfuric acid and mixed with an aqueous so-lution of 4.2 g sodium nitrite. The resultant reddish-brown suspension of the dizonium salt is dropped with stirring into a solution of 9.3 g ferrocene in 20 ml concentrated sulfuric acid and 150 ml water. Subse-, lZ~9~
quently, the suspension thus obtained is stirred at room temperature, and the precipitate is sucked off, washed and dried. Yield: 9.1 g.
b) Reaction with Pyrrole 3 g ferrocenyl polystyrene is mixed with 1.1 g pyrrole in acetonitrile and oxidized by dropwise adding 17.2 g iron-III-prechlorate dissolved in 25 ml acetonitrile. 0 The product is stirred into 500 ml methanol, sucked off and washed until the filtrate is colorless. Yield after drying: 4.4 g. Conductivity: 1 S/cm.
Exam~le 3 3 g of a poly-(4-vinylpyridine)iron-III-chloride complex is mixed with 1.28 g lithium perchlorate and 1.07 g pyrrole in acetonitrile and oxidized by dropwise adding 5.2 g iron-III-chloride complex is mixed with 1.28 g lithium perchlorate and 1.07 g pyrrole in acetonitrile and oxidized by dropwise adding 5.2 g iron-III-chloride dissolved in 20 ml acetonitrile. The precipitating polymer product is sucked off, washed with acetonitrile and CH2Cl2 and dried. Yield: 3.85 g. Conduc-tivity: 8 x 10 3 S/cm.
Exam~le 4 1.2 g ferrocene is dissolved with 1 g AlCl3 in dichloro-ethane, mixed with 6 g polyethyl methacrylate in dichlo-roethane, and refluxed for one hour. After cooling, the solution is poured into ice water, acidified by dilute HCl, the organic phase is separated in the separating ~2~
funnel and concentrated by evaporation. The polymer is precipitated bv pouring into methanol, washed with methanol and dried.
6 g ferrocenyl ethyl methacrylate is dissolved in ace-tonitrile with 1 g pyrrole, and a 10-% Fe(ClO4)3 solution in acetonitrile is added dropwise, until visible reac-tions do not occur any longer. The polymer product is precipitated by pouring into methanol, washed and dried.
Yield: 7.2 g. Conductivity: 0.2 S/cm. The material is flëxible and has some thermoplastic properties.
Example 5 5 % vinylferrocene, 90 % ethyl acrylate and 5 % acrylic acid are copolymerized with 0.5 % azoisobutyronitril at 82 C. The polymer is dissolved in acetonitrile, mixed with 10 wt. % pyrrole and oxidized with a 10-% iron-III-perchlorate solution in acetonitrile. The product is precipitated by pouring into methanol, washed with water and ethanol, and dried. Conductivity:
0.2 S/cm.
Exam~le 6 4 g of polyvinyl alcohol-vinyl acetate copolymer is dissolved in 40 ml methylene chloride and 2 g anhy-drous pyridine. After addition of 2 g ferrocenecar-boxylic acid chloride in 10 ml CH2Cl2 the mixture is stirred for one hour at room temperature. Subse-quently, the mixture is stirred into water and ex-tracted with methylene chloride. Drying over sodium sulfate, filtration and drawing off the solvent yields an amber-colored polymer.
i 35 ~9~
This polymer is dissolved in 250 ml methylene chloride/
acetonitrile at a ratio of 1 : 1 and with stirring mixed first with 0.5 g pvrrole and then with 8 g Fe(C104)3 dissolved in 10 ml acetonitrile. A black solution is obtained, from which the copolymer slowly precipitates.
The precipitation is completed by drawing off the CH2C12 and pouring the residue into water. The black polymeric product is washed several times and dried. It is flexible and has some thermoplastic properties. Con-ductivity: 0.8 S/cm.
Description The invention concerns copolymers and blends with conjugated ~ system, methods for their production and their application.
s Polymers with conjugated ~ system, which become elec-trically conductive after doping, i. e. oxidation or reduction, can also be regarded as redox-active polymers. Oxidation or reduction of these materials means electron loss or gain by the ~ electron system of the main chain. The resultant charges are delocalized over wide ranges of ~ conjugation. They can migrate or jump along or between the chains, thus causing charge transport and thus conductivity upon application of an electric field. Electronically, thev change the band structure from the semiconducting or insulating state of the undoped polymer to that of a metal with extended partly filled band at the Fermi limit. Structurally, they form rigid microcrystalline regions which are de-trimental to all properties typical of plastics and to all mechanical and processing properties. An in-trinsically conductive polymers of this type can neither be dissolved nor melted and can only be used in the form which it adopts after doping. In order to obtain nevertheless mechanically suitable and pro-cessible electrically conductive polymers, polymers with conjugated ~ system have to be blended as block or graft copolymers or as blends with conventional macromolecules forming flexible soft segments. High conductivity, combined with good mechanical properties and processibility, is always achieved if the maximum possible homogenous distributlon of the conductive component in the matrix of the conventional polymer ~2~9~
is reached. Copolymers and blends of polyacetylene of this type are already known (Galvin and Wnek, J. of Polym.
Sci., Polym. Chem. Ec. 21, 2727 (1983); Lee and Jopson, Makrom. Chem. Rapid Commun. 4, 375 (1983)). With concen-trations as low as 5%, conductivities are reached whichare by a maximum of one to two orders of magnitude below the conductivity of pure polyacetylene. The oxidatively doped conductive polyacetylene, however, has the drawback to decompose on storage and in air, thus losing its conductivity.
It is the object of the present invention to produce intrinsically conductive polymers which are stable and have optimum processing properties.
According to the invention, this aim is reached by the fact that the copolymers and blends are essentially composed of polymeric components (A) without conjugated~
system and of polymeric components (B) with conjugated~
system, the component A containing redox-active groups which, in oxidized or reduced state, have an active potential that is sufficient for oxidation or reduction of the component ~.
In the methods of producing suc'n copolymers and blends according to the invention, redox-active compounds are homo- or copolymerized with polymerizable substituents or attached to polymers without conjugated ~ system in 3 known manner by chemical reaction, and the polymeric component A which is thus obtained is mixed in a known manner with the polymeric component B or with the monomer forming the component B, or chemically or electrochemically oxidized or reduced.
~' ~z~
The copolymers and blends according to the invention are suitable in particular as conductors or semiconductors, in solar cells, for antistatic finish of plastics, as materials of low surface resistance, suitable for capac-itive scanning, as materials for electromagnetic shield-ing, as battery electrodes, as electrode materials and as membranes for electrochemistry and fuel cells.
The invention permits in particular polypyrrole, polythio-phene and derivatives, such as substituted polypyrroles or polythiophenes, polymers consisting of aromatic rings, pyrrole and/or thiophene units, as well as polyanilines which are obtained by oxidative polymerization of aniline, to be processed with non-conductive polymers ~'10 S/cm) in a wide range of variation to give copolymers or blends.
Almost all conventional polymers, especially those with flexible or highly mobile chain forms, can be processed as copolymers with polypyrrole to give electrically conductive plastics. This is possible on condition that redox-active groups are present, which can be either attached as side-chain substituents or incorporated by polymerization into the main chain as a difunctional monomer. Suitable redox-active groups are in particular such groups which can be oxidized and reduced with high reversibility and whose oxidation potentials are slightly above that of the poly-mers with conjugated ~ system. For polypyrrole, polyani-line and polymers composed of alternating aromatic and pyrrole rings, this is ideally reached by the dicyclopenta-dienyliron or ferrocene complex.
,~
~69~
The ferrocene complex can be reversibly oxidized at about + 0.4 to 0.5 V versus saturated colomel electrode and is capable in this form, i. e. as ferricinium salt, to oxidize the above polymers with conjugated ~ .ystem and to ma~e them conductive.
Polypyrrole, for example, has an oxidation potential of -0.2 V versus saturated colomel electrode and poly-aniline has an oxidation potential of +0.1 V versus SCE.
In the reaction with polymer-bonded ferricinium salt, electrons are transferred to the ferrocene, and anions to the polymer with conjugated ~ system:
I Fel CiO4 - +
CH ~ CH ~
I ~ C~04 -25 Nevertheless, ferrocene as redox-active group in a blend consisting of polyphenylene pyrrole or poly-naphthalene pyrrole, permits electron and ion migration even in the non-conductive part, thus causing fast and uniform doping of the conjugated polymer, which is not limited to freely accessible parts of the conductive component.
An essential feature of the invention is the bond of the ferrocene vla substituents or directly to the cy-3~Z6~
clopentadienyl rings as substituent to the side chain of a conventional polymer, or a polymer in which a disubstituted ferrocene monomer is incorporated in the main chain by polycondensation, polyaddition or aromatic substitution at the cyclopentadienvl rings.
Bonding as side-chain substituent is possible, for example, by reacting polyvinyl chloride, polybuta-diene, polyacrylate, polymethacrylate, copolymers from maleic anhydride and styrene, copolymers from butadiene and styrene, chloromethylated polystyrene or the like with AlCl3 and unsubstituted ferro-cene. Depending on the ferrocene concentration, on the use of AlCl3, in the temperature and on the course of reaction, weakly substituted non-cross-linked or highly substituted cross-linked polymers are ob-tained. Bonding of the ferrocene can also be achieved by diazotization of the poly-p-aminostyrene and subse-quent reaction with ferrocene of ferricinium salts, by reaction of the ferrocenecarboxylic acid chloride with polymers containing NH2 or OH groups, e. g. polyvinyl alcohol and copolymers such as partially hydrolyzed polyvinyl acetate or polyvinyl butyral, and in addition poly (1-hydroxypropene-(2)), polyhydroxyethyl- or hydro-xypropyl acrylate or methacrylate and copolymers there poly(1-aminopropene-(2)), poly(p-aminostyrene), poly (p-amino-o~-methylstyrene), polyvinyl amine and copoly-mers thereof, as well as copolymers of aminopropyl-triethoxysilane and siloxane oligomers.
It is also possible to attach hydroxylkyl ferrocene to copolymers which contain carboxylic acid chloride, sulfonic acid chloride or anhydride substituents, or by esterification of copolymers of acrylic acid.
~5 ~Z~91Q4 Introduction of the ferrocene molecule into the side chain of polymers is also possible by mono- or copoly-merization of monomers which contain the ferrocene ring with substituted polymerizable group. Candidates for this procedure include vinyl and divinyl ferrocene, ferrocenyl methyl methacrylate or acrylate, ferrocenyl methyl arcylamide, ethimylferrocene, p-ferrocenyl styrene, p-ferrocenyl phenylacetylene, etc.
Incorporation of ferrocene into the main chain can be achieved, for example, by polycondenzation or poly-addition with appropriate sutstituents. It is possible, e. g., to react terminally diamino- or dihydroxy-substituted monomers or prepolymers with ferrocene-dicarboxylix acid, dicarboxylic acid esters or dicarboxylic acid chloride, ferrocene diisocyanate or ferrocene dialkyl oxirane.
Inversely, dihydroxyalkvl ferrocenes can be reacted with monomeric dicarboxylix acids or polyesters with terminal carboxyl groups, with monomeric or oligo-meric diisocyanates or prepolymeric epoxy resins to give polymers with ferrocene complex in the main chain.
Like ferrocenes, it is also possible according to the invention to use other transition metal complexes, f F II/III CoII/III and RuII/III, which are attached to a polymer chain via ligands and shows reversible redox behavior. 0 Iron, cobalt or ruthenium salts complexed by poly(4)-(or-2-)-vinylpyridine or polyvinylbipyridine, for example, are suitable. According to the invention, it is possible to use polymer-bonded metal salicylates, 5 12~
metal salicylaldehvde, metal salicyl-aldehydimine complexes, Pfeiffer complexes complexed via amino acids, and the like. Preferably, polymer-bonded metal oxinates metal glyoximates, metal porphyrin and metal phthalocvanine complexes can be used. In this context, an anodic polymerizate of pyrrole and tetrasulfonated phthalocyanine iron complex (R.A.
Bull, F.R. Fan, A.J. Bard, J. Electrochem. Soc. ABC
1636, 1983) is known. In this case, however, the redox-active complex is directly incorporated in polypyrrole and not coupled with another conventional polymer.
According to the invention, also polymers with rever-sibly oxidizable and recudible organic groups can be used for the production of copolymers or blends.
In particular, polymers with quinoidal systems in main and side chains can be used, e. g. a polybenzoquinone-tetracarboxylic acid anhydride which reacts with hexa-methylenediamine to give benzoquinone main-chain poly-mers or with poly-p-aminostyrene to give side-chain polymers.
For combining the described redox-active polymers with polymers which contain a conjugated ~-electron system, it is necessary to harmonize the oxidation and reduction potentials.
The electroactive state of the polymer with isolated redox-active groups can only be utilized if the oxi-dation potential of the polvmer with conjugated ~
system is lower, or its reduction potential is higher that that of the copolymers. The polymer with redox-~26~
active groups must be able either in oxidized state to oxidize the conjugated polymer and thus make it electronically conductive, or in reduced state to reduce a polymer with conjugated ~ system.
~olymer-bonded ferrocene, therefore, can be ideally used as copolymer or blend for polypyrrole, which they cannot polymerize but oxidize and make conductive.
These polypyrrole blends are prepared according to the invention by oxidizing a homogenous mixture of a dissolved or swollen ferrocene polymer together with pyrrole, either anodically or chemically.
Electrochemically, at potentials of +0.4 to 0.6 V
versus saturated colomel electrode, the ferrocene units are first oxidized to positively charged ferricene units, whereas at 0.9 to 1.1 V polymeri-zation of pyrrole stars. As soon as the polypyrrole has reached a specific length of conjugation it is oxidized by ferricene into the conductive form, with electron and ion transfer. ~niform dustribution of ferrocene in the matrix of the conventional polymer is a prerequisite for an equally homogenous distri-bution of the polypyrrole. About 5 wf % or 1 to 2 mole % ferrocene is sufficient in the case of uniform distribution to generate conductivities of 10 2 to S/cm with about 4 to 8 mole % polypyrrole.
According to the invention, the contents of the redox-active component and the concentration of the conductive polymer are variable within a wide range from about 1 to 90 %. For the electrochemical pro-duction, solvents such as acetonitrile, propylene carbonate, nitromethane, dioxane, 1,2-dimethoxyethane, N-methylpyrrolidone, hexamethyl phosphoric acid triamide ~26~
g or the like are suitable at low water content, together with the tetraalkyl ammonium or lithium salts which are soluble therein. The polvmerization of pyrrole and the production of blends is also possible from acid aqueous solution. The anions must be resistant to oxidation and must not be below a minimum size. ~F4, C104, AsF6, SbF6, PF6, SbC16, NO3, ReO4, TaF 6' HSO4, for example, as well as organic benzene or alkane sulfonic acid anions are suitable. According to the invention, blends of ferrocene polymers and poly-pyrrole can also be produced by chemical oxydation. This is achieved preferably by iron-III salts in pure organic or aqueous/organic solution or dispersion. FeC13 or Fe(C104)3 . 9 H20, but also other oxidants such as bichromate or H202 solution, are suited for this purpose.
Reaction with the ferrocene polymer/pyrrole mixture is preferably effected in acetonitrile or in the two-phase system methylene chloride/water.
A special variant of this invention consists in using a copolymer with ferrocenyl and carboxylic acid or sul-fonic acid substituents, in which - on oxidation - the charges of the oxidized ferrocene and of the polypyrrole can be compensated by the acid anions of the polymer.
According to the invention, this can be achieved by chemical oxidation by iron-III-acetylacetonate or by electrochemical oxidation, protons and electrons being released by the polymer.
While polymer-bonded ferrocenes have sufficiently high oxidation potentials for polypyrrole and polyaniline, polymer-bonded iron-III, cobalt-III or ruthenium-III 5 ~Z69~
complexes of higher electrochemical potential are necessary for polvthiophene. Similarly, N-phenyl-substituted pyrroles can only be satisfactorily pro-cessed to copolymers or blends with these materials.
The process is equal to that used for the production of blends from polvpyrrole and ferrocene polymers.
The copolymers and blends according to the invention show good mechanical and application-technological properties. They can be processed either from the solution during production or thermoplastically molded into various shapes. If appropriate copolymers and ferrocene concentrations are selected, they can be processed into shapes with smooth surface of high electrical conductivity. They can thus be used for applications involving the electrooptical or capa-citive scanning of a surface structure. In this respect, they are also superior to black- or metal-filled plastics.
Another important application is the use of the co-polymers according to the invention as battery of fuel cell electrodes. This possible since a highly rever-sible redox system is combined with a conductive poly-mer. Oxidation and reduction cycles of the redox-active component can be used ideally for electro-chemical storage purposes. While the electrochemical-catalytic effect is used in fuel cells, it is also possible to use the copolymers and blends as chemical catalysts with active transition metal centers. Further applications are as conductors or semiconductors of low density, as materials for electromagnetic shielding, as solar cells or for antistatic finish of plastics.
~Z~
Examole _ a) Preparation of Ferrocenyl Butadiene 8.5 g AlCl3 is dissolved in 200 ml dichloroethane, then 46.5 g ferrocene is added, and 5~ g Lithene PM (Metall-gesellschaft) dissolved in 200 ml dichloroethane is added dropwise. After stirring for two hours at room temperature, the reaction mixture is poured into 600 ml methanolic HCl, the polymer is separated by filtration, washed and dried. The starting polymer is first oxidized with FeCl3 in nitromethane, washed and then used for preparing the blend.
b) Reaction with Pyrrole Ferrocenyl butadiene in oxidized form is swollen in di-chloroethane together with pyrrole and subsequently reaction with aqueous iron-III-perchlorate solution in a two-phase reaction. The resultant blend is pre-cipitated with methanol, washed and dried. It shows thermoplastic properties and elastic behavior. Con-ductivity: 10 2 S/cm.
Example 2 a) Preparation of Ferrocenyl Polystyrole 6 g poly-p-aminostyrene is suspended in 100 ml 10-%
aqueous sulfuric acid and mixed with an aqueous so-lution of 4.2 g sodium nitrite. The resultant reddish-brown suspension of the dizonium salt is dropped with stirring into a solution of 9.3 g ferrocene in 20 ml concentrated sulfuric acid and 150 ml water. Subse-, lZ~9~
quently, the suspension thus obtained is stirred at room temperature, and the precipitate is sucked off, washed and dried. Yield: 9.1 g.
b) Reaction with Pyrrole 3 g ferrocenyl polystyrene is mixed with 1.1 g pyrrole in acetonitrile and oxidized by dropwise adding 17.2 g iron-III-prechlorate dissolved in 25 ml acetonitrile. 0 The product is stirred into 500 ml methanol, sucked off and washed until the filtrate is colorless. Yield after drying: 4.4 g. Conductivity: 1 S/cm.
Exam~le 3 3 g of a poly-(4-vinylpyridine)iron-III-chloride complex is mixed with 1.28 g lithium perchlorate and 1.07 g pyrrole in acetonitrile and oxidized by dropwise adding 5.2 g iron-III-chloride complex is mixed with 1.28 g lithium perchlorate and 1.07 g pyrrole in acetonitrile and oxidized by dropwise adding 5.2 g iron-III-chloride dissolved in 20 ml acetonitrile. The precipitating polymer product is sucked off, washed with acetonitrile and CH2Cl2 and dried. Yield: 3.85 g. Conduc-tivity: 8 x 10 3 S/cm.
Exam~le 4 1.2 g ferrocene is dissolved with 1 g AlCl3 in dichloro-ethane, mixed with 6 g polyethyl methacrylate in dichlo-roethane, and refluxed for one hour. After cooling, the solution is poured into ice water, acidified by dilute HCl, the organic phase is separated in the separating ~2~
funnel and concentrated by evaporation. The polymer is precipitated bv pouring into methanol, washed with methanol and dried.
6 g ferrocenyl ethyl methacrylate is dissolved in ace-tonitrile with 1 g pyrrole, and a 10-% Fe(ClO4)3 solution in acetonitrile is added dropwise, until visible reac-tions do not occur any longer. The polymer product is precipitated by pouring into methanol, washed and dried.
Yield: 7.2 g. Conductivity: 0.2 S/cm. The material is flëxible and has some thermoplastic properties.
Example 5 5 % vinylferrocene, 90 % ethyl acrylate and 5 % acrylic acid are copolymerized with 0.5 % azoisobutyronitril at 82 C. The polymer is dissolved in acetonitrile, mixed with 10 wt. % pyrrole and oxidized with a 10-% iron-III-perchlorate solution in acetonitrile. The product is precipitated by pouring into methanol, washed with water and ethanol, and dried. Conductivity:
0.2 S/cm.
Exam~le 6 4 g of polyvinyl alcohol-vinyl acetate copolymer is dissolved in 40 ml methylene chloride and 2 g anhy-drous pyridine. After addition of 2 g ferrocenecar-boxylic acid chloride in 10 ml CH2Cl2 the mixture is stirred for one hour at room temperature. Subse-quently, the mixture is stirred into water and ex-tracted with methylene chloride. Drying over sodium sulfate, filtration and drawing off the solvent yields an amber-colored polymer.
i 35 ~9~
This polymer is dissolved in 250 ml methylene chloride/
acetonitrile at a ratio of 1 : 1 and with stirring mixed first with 0.5 g pvrrole and then with 8 g Fe(C104)3 dissolved in 10 ml acetonitrile. A black solution is obtained, from which the copolymer slowly precipitates.
The precipitation is completed by drawing off the CH2C12 and pouring the residue into water. The black polymeric product is washed several times and dried. It is flexible and has some thermoplastic properties. Con-ductivity: 0.8 S/cm.
Claims (33)
1. Copolymers and blends essentially composed of polymeric components (A) without conjugated .pi. system and of polymeric components (B) with conjugated .pi. system, wherein the component A contains redox-active groups which possess an active potential in oxidized or reduced state, which is sufficient for the oxidation or reduction of the component B.
2. Copolymer.s and blends as claimed in claim 1, wherein the component A contains, as redox-active groups, .sigma. or .pi.
complexes or chelates which are incorporated in the main chain and/or in the side chains.
complexes or chelates which are incorporated in the main chain and/or in the side chains.
3. Copolymers and blends as claimed in Claim 1, wherein the component A contains, as redox-active groups, .sigma. or .pi.
complexes or chelates of transition metals which are incorporated in the main chain and/or in the side chains.
complexes or chelates of transition metals which are incorporated in the main chain and/or in the side chains.
4. Copolymers and blends as claimed in Claim 1, 2 or 3, wherein FeIII/II,CoIII/II and/or RUIII/II complexes are contained as transition metal complexes.
5. Copolymers and blends as claimed in Claim 1, 2 or 3, wherein ferrocene complexes are contained as transition metal complexes.
6. Copolymers and blends as claimed in Claim 1, 2 or 3, which contain metal salicylates, metal salicylaldehyde, metal salicylaldehydimine complexes, Pfeiffer complexes complexed via amino acids, metal oxinates, metal glyoxi-mates, metal porphyrin and metal phthalocyanine complexes as metal complexes.
7. Copolymers and blends as claimed in Claim 1, wherein the component A contains quinoid systems, as redox-active groups which are incorporated in the main chain and/or in the side chains.
8. Copolymers and blends as claimed in Claim 7, wherein the quinoid system is benzoquinone.
9. Copolymers and blends as claimed in Claim 1, 2 or 3, wherein the component A is substituted with anion-forming groups.
10. Copolymers and blends as claimed in Claim 1, 2 or 3, wherein the component A is substituted with carboxylic acid and/or sulfonic acid or anhydride groups.
11. Copolymers and blends as claimed in Claim 1, 2 or 3, wherein mono- and copolymers of substituted or unsubstituted pyrrole, thiophene and/or aniline are used as component B.
12. Copolymers and blends as claimed in Claim 1, 2 or 3, wherein the component B consists of -C=C-, -C?C-, -N=N-, -C=N- units, mononuclear or polynuclear aromatic substances and substituted or unsubstituted pyrrole, thiophene and/or aniline rings.
13. Copolymers and blends as claimed in Claim 1, 2 or 3, wherein oxidatively polymerized, unsubstituted pyrrole is used as component B.
14. Copolymers and blends as claimed in Claim 1, wherein substituted polypyrroles or copolymers of substituted and unsubstituted pyrroles are used as component B.
15. Copolymers and blends as claimed in Claim 14, wherein the pyrroles are substituted in N-position with alkyl groups, alkinyl groups and/or in 3-position with alkyl groups, alkinyl groups, alkoxy groups, and halogen groups, as well as in 3,4-position with alkyl groups, alkinyl groups, alkoxy groups and halogen groups with 1 to 6 C
atoms.
atoms.
16. Copolymers and blends as claimed in Claim 15, wherein the pyrroles are substituted in N-position with alkyl groups, alkinyl groups and/or in 3-position with alkyl groups, alkinyl groups, alkoxy groups, and halogen groups, as well as in 3,4-position with alkyl groups, alkinyl groups, alkoxy groups and halogen groups with 1 to 3 C
atoms.
atoms.
17. Method of producing copolymers and blends as defined in Claim 1, wherein redox-active compounds containing polymerizable substituents are homo- or copolymerized or attached to polymers without conjugated .pi. system by chemical reaction and the polymeric component A thus obtained is mixed with the polymeric component B or with the monomer forming the component B, and then chemically or electrochemically oxidized or reduced.
18. Method as claimed in Claim 17, wherein a transition metal complex is used as redox-active compound.
19. Method as claimed in Claim 18, wherein the transition metal complex is ferrocene.
20. Method as claimed in Claim 17, 18 or 19, wherein substituted or unsubstituted polypyrrole, polythiophene or polyaniline and their copolymers are used as the polymeric component B.
21. Method as claimed in Claim 17, 18 or 19, wherein, in order to produce the polymeric component A, unsubstituted ferrocene is reacted with a polymer without conjugated system.
22. Method as claimed in Claim 17, 18 or 19, wherein, in order to produce the polymeric component A, unsubstituted ferrocene is reacted with polyvinyl chloride, polybuta-diene, polyacrylate, polymethacrylate, copolymers of maleic anhydride and styrene, copolymers of butadiene and styrene, or chloromethylated polystyrene.
23. Method as claimed in Claim 17, 18 or 19, wherein, to produce the polymeric component A, ferrocene or ferricinium salts are reacted with diazotized poly-p-aminostyrene.
24. Method as claimed in Claim 17, 18 or 19, wherein, to produce the polymeric component A, ferrocenecarboxylic acids, anhydrides or chlorides or ferrocene alkylcarboxylic acids, anhydrides or chlorides are reacted with polymers containing NH2 or OH groups.
25. Method as claimed in Claim 17, 18 or 19, wherein, to produce the polymeric component A, ferrocenecarboxylic acids, anhydrides or chlorides are reacted with polyvinyl alcohol and copolymers.
26. Method as claimed in Claim 17, 18 or 19, wherein, to produce the polymeric component A, ferrocenecarboxylic acids, anhydrides or chlorides are reacted with partially hydrolyzed polyvinyl acetate or polyvinyl butyral.
27. Method as claimed in Claim 17, 18 or 19, wherein, to produce the polymeric component A, ferrocene with polymer-izable substituents, vinyl and divinyl ferrocene, ferro-cenyl acrylate and methacrylate, alkylferrocenyl acrylate and methacrylate, ferrocenyl methyl acrylamide, ethinyl-ferrocene, p-ferrocenyl styrene, p-ferrocenyl phenylacetyl-ene, is homo or copolymerized with conventional vinyl monomers.
28. Method as claimed in Claim 17, 18 or 19, wherein, to produce the polymeric component A, dihydroxyalkyl ferro-cenes are reacted with monomeric or oligomeric diisocyan-ates or prepolymeric epoxy resins, with monomeric dicarboxylic acids, or with polyesters with carboxyl terminal groups.
29. Method as claimed in Claim 17, 18 or 19, wherein, to produce the polymeric component A, terminally diamino- or dihydroxy-substituted monomers or prepolymers are reacted with ferrocenedicarboxylic acids, dicarboxylic acid esters, dicarboxylic acid chlorides or other active dicarboxylic acid derivatives, ferrocene diisocyanate or ferrocene dialkyl oxirane.
30. Method as claimed in Claim 17, 18 or 19, wherein pyrrole, thiophene or aniline are homogenously mixed with the dissolved and swollen component A and anodically or chemically oxidized.
31. Method as claimed in Claim 17, 18 or 19, wherein the polymeric component A contains carboxylic acid groups and/or sulfonic acid or sulfonic anhydride groups, which are converted into carboxylate and/or sulfoxylate ions by oxidation.
32. Method as claimed in Claim 17, 18 or 19, wherein the polymeric component A is oxidized prior to mixing with the polymeric component B.
33. Application of copolymers and blends as claimed in Claim 1, 2 or 3 as conductors or semiconductors, in solar cells, for antistatic finish of plastics, as materials of low surface resistance, suitable for capacitive scanning, as materials for electromagnetic shielding, as battery electrodes, as electrode materials and as membranes for electrochemistry and fuel cells.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3419788.5 | 1984-05-26 | ||
| DE19843419788 DE3419788A1 (en) | 1984-05-26 | 1984-05-26 | COPOLYMERS AND BLENDS OF POLYMERS WITH A CONJUGATED (PI) SYSTEM |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1269194A true CA1269194A (en) | 1990-05-15 |
Family
ID=6236989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000481074A Expired - Lifetime CA1269194A (en) | 1984-05-26 | 1985-05-08 | Copolymers and blends of polymers with conjugated p- system |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0185063A1 (en) |
| JP (1) | JPS61502261A (en) |
| CA (1) | CA1269194A (en) |
| DE (1) | DE3419788A1 (en) |
| WO (1) | WO1985005728A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5520849A (en) * | 1988-09-16 | 1996-05-28 | The Dow Chemical Company | Electrically conductive polymer composition |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI74715C (en) * | 1985-07-24 | 1988-03-10 | Neste Oy | ELEVATED POLYTIOFEN OCH FOERFARANDE FOER DESS FRAMSTAELLNING OCH ANVAENDNING. |
| JPH0784553B2 (en) * | 1986-11-26 | 1995-09-13 | 三井東圧化学株式会社 | Aromatic compound polymer composite film and method for producing the same |
| GB8714239D0 (en) * | 1987-06-17 | 1987-07-22 | Dowty Mining Machinery Ltd | Solid state batteries |
| FI82702C (en) * | 1987-07-29 | 1991-04-10 | Neste Oy | Non-conductive plastic composites containing poly (3-alkylthiophene) |
| GB2210044A (en) * | 1987-09-16 | 1989-06-01 | Dow Chemical Gmbh | Electrically conductive polymer compositions and polymers useful for preparing the polymer compositions |
| US5151224A (en) * | 1988-05-05 | 1992-09-29 | Osaka Gas Company, Ltd. | Tetrasulfonated metal phthalocyanine doped electrically conducting electrochromic poly(dithiophene) polymers |
| US4877646A (en) * | 1988-06-27 | 1989-10-31 | Milliken Research Corporation | Method for making electrically conductive textile materials |
| JP2922521B2 (en) * | 1988-10-06 | 1999-07-26 | 昭和電工株式会社 | Solid electrolytic capacitors |
| FI890427A (en) * | 1989-01-27 | 1990-07-28 | Neste Oy | BRUK AV EN ELLEDANDE POLYMER COMPOSITES. |
| FR2698631B1 (en) * | 1992-12-01 | 1995-02-10 | Centre Nat Rech Scient | Copolymers with redox properties and their use for the preparation of materials with mixed conduction. |
| KR950013182B1 (en) * | 1992-05-27 | 1995-10-25 | 국방과학연구소 | Conductive polymer composite having high active electrical density and its manufacture method |
| US5388025A (en) * | 1992-09-01 | 1995-02-07 | Motorola, Inc. | Rechargeable electrical energy storage device having organometallic electrodes |
| DE102009020544A1 (en) | 2009-05-08 | 2010-11-11 | Heinrich-Heine-Universität Düsseldorf | Preparing a copolymer, useful to produce e.g. plastics, comprises providing a cyclodextrin compound, providing a metallocene compound with double bonds and providing a styrene compound, adding an initiator and polymerizing components |
| WO2012121417A1 (en) * | 2011-03-09 | 2012-09-13 | Waseda University | Conducting polymer / redox polymer blends via in-situ oxidative polymerization - preparation methods and application as an electro-active polymeric materials |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3049551A1 (en) * | 1980-12-31 | 1982-07-29 | Basf Ag, 6700 Ludwigshafen | ELECTRICALLY CONDUCTIVE POLY (PYRROL) DERIVATIVES |
| DE3130497A1 (en) * | 1981-07-23 | 1983-02-10 | Basf Ag, 6700 Ludwigshafen | METHOD FOR THE PRODUCTION OF AIR-STABLE, ELECTRICALLY CONDUCTIVE, POLYMERIC POLYESYSTEMS AND THEIR USE IN ELECTROTECHNICS AND FOR THE ANTISTATIC EQUIPMENT OF PLASTICS |
| DE3223545A1 (en) * | 1982-06-24 | 1983-12-29 | Basf Ag, 6700 Ludwigshafen | PYRROL COPOLYMERS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
-
1984
- 1984-05-26 DE DE19843419788 patent/DE3419788A1/en active Granted
-
1985
- 1985-04-26 WO PCT/EP1985/000189 patent/WO1985005728A1/en not_active Application Discontinuation
- 1985-04-26 JP JP60502686A patent/JPS61502261A/en active Pending
- 1985-04-26 EP EP85902972A patent/EP0185063A1/en not_active Withdrawn
- 1985-05-08 CA CA000481074A patent/CA1269194A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5520849A (en) * | 1988-09-16 | 1996-05-28 | The Dow Chemical Company | Electrically conductive polymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61502261A (en) | 1986-10-09 |
| EP0185063A1 (en) | 1986-06-25 |
| WO1985005728A1 (en) | 1985-12-19 |
| DE3419788C2 (en) | 1988-02-04 |
| DE3419788A1 (en) | 1985-11-28 |
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